US11047065B2 - Method for producing silicon single crystal, heat shield, and single crystal pulling device - Google Patents
Method for producing silicon single crystal, heat shield, and single crystal pulling device Download PDFInfo
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- US11047065B2 US11047065B2 US16/471,805 US201716471805A US11047065B2 US 11047065 B2 US11047065 B2 US 11047065B2 US 201716471805 A US201716471805 A US 201716471805A US 11047065 B2 US11047065 B2 US 11047065B2
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- heat shield
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052710 silicon Inorganic materials 0.000 title claims description 34
- 239000010703 silicon Substances 0.000 title claims description 34
- 239000013078 crystal Substances 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title description 7
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 149
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims description 74
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 230000005499 meniscus Effects 0.000 description 14
- 238000009826 distribution Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 5
- 238000004781 supercooling Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 108010053481 Antifreeze Proteins Proteins 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
- C30B15/203—Controlling or regulating the relationship of pull rate (v) to axial thermal gradient (G)
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/20—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/14—Heating of the melt or the crystallised materials
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/30—Mechanisms for rotating or moving either the melt or the crystal
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
Definitions
- the present invention relates to a method of producing a monocrystalline silicon, a heat shield, and a monocrystal pull-up apparatus.
- a temperature difference between a dopant-added melt, in which red phosphorus is added to a silicon melt, and a seed crystal is set in a range of 50 to 97 K when the seed crystal is brought into contact with the dopant-added melt.
- the distance between a heat-shielding plate and dopant-added-melt liquid surface is set in a range of 20 mm to 30 mm at the start of a growth period of a straight body of a monocrystalline silicon and in a range of 6 mm to 15 mm during a growth period of a part of the straight body remote from a border between a shoulder and the straight body by 200 mm in a direction opposite a pulling direction.
- Patent Literature 1 Japanese Patent No. 5420548
- dislocation sometimes occurs due to compositional supercooling at a bottom portion of a monocrystalline silicon (a part of a straight body whose solidification rate is 60% or more, where the solidification rate at an upper end of the straight body is defined as 0% and the solidification rate at a lower end of the straight body is defined as 100%) according to the method disclosed in Patent Literature 1.
- a producing method capable of more effectively reducing occurrence of dislocation has been desired.
- An object of the invention is to provide a method of producing a monocrystalline silicon capable of reducing occurrence of dislocation, a heat shield, and a monocrystal pull-up apparatus.
- a method of producing a monocrystalline silicon uses a monocrystal pull-up apparatus including: a crucible configured to receive a dopant-added melt including a silicon melt and red phosphorus added to the silicon melt; a crucible driver configured to vertically move and rotate the crucible; a pull-up portion configured to pull up a seed crystal after bringing the seed crystal into contact with the dopant-added melt to grow the monocrystalline silicon; a heat shield disposed above the crucible to surround the monocrystalline silicon, a lower end portion of the heat shield being in a form of a circular hollow cylinder; and a chamber configured to house the crucible and the heat shield, the method including: growing the monocrystalline silicon using the heat shield satisfying a formula (1) below, R ⁇ 1.27 ⁇ C (1)
- C represents a radius (mm) of a straight body of the monocrystalline silicon
- R represents an inner radius (mm) of the heat shield at the lower end portion thereof.
- the heat shield satisfying the formula (1) is used. Since the distance between an outer periphery of the monocrystalline silicon and an inner periphery of the lower end portion of the heat shield is reduced to be shorter than a predetermined value, heat dissipation from the dopant-added melt through the gap between the monocrystalline silicon and the lower end of the heat shield can be reduced, thus increasing the temperature gradient at the bottom portion of the monocrystalline silicon in the pulling direction as compared with an instance where the formula (1) is not satisfied. Accordingly, the occurrence of dislocation due to compositional supercooling can be restrained.
- the “lower end portion in a form of a circular hollow cylinder” may be exemplified by a downwardly flared or tapered hollow truncated cone, a cylinder of constant diameter at any vertical position thereof, a combination of a hollow truncated cone and a cylinder, and a combination of a tapered hollow truncated cone and a flared hollow truncated cone.
- the heat shield is provided with at least one cut recessed from an inner periphery of the lower end portion of the heat shield toward an outer periphery thereof.
- the above arrangement allows the dopant-added melt to be exposed through the cut in a top plan.
- a sufficient liquid-surface exposure area for checking a height of the liquid surface can be ensured.
- the crucible can be moved upward so that the distance between the liquid surface of the dopant-added melt and the lower end of the heat shield becomes at a predetermined value during the growth of the monocrystalline silicon, thereby keeping thermal hysteresis and impurity (e.g. oxygen) concentration constant in each of batches of monocrystalline silicon and producing monocrystalline silicon of stable quality.
- impurity e.g. oxygen
- the heat shield further satisfies formulae (2) and (3) below, 0.926 ⁇ R/A (2) R/A ⁇ 0.969 (3)
- A represents a distance (mm) from a center of the lower end portion of the heat shield to a radially deepest portion of the lower end portion at the cut in a top plan.
- the dislocation may occur at a top portion (a region of the straight body with a solidification rate ranging from 0% to 20%, and the shoulder) of the monocrystalline silicon due to an influence of the remelt growth area Q.
- the heat shield further satisfies formulae (4) and (5) below, 0.051 ⁇ H/L (4) H/L ⁇ 0.070 (5)
- H represents a maximum width (mm) of the cut in a top plan
- L represents a length (mm) of an inner circumference of the lower end portion of the heat shield assuming that the cut is not present.
- H represents a sum of the maximum widths of the plurality of cuts.
- the at least one cut is a single cut.
- the maximum width of the cut can be increased to secure a sufficient liquid-surface exposure area as compared with an instance in which the plurality of cuts are provided. Consequently, the height of the liquid surface of the dopant-added melt can be easily checked.
- the method of producing a monocrystalline silicon it is preferable that, in growing the monocrystalline silicon, an image of a liquid surface of the dopant-added melt exposed through the cut is captured, a height of the liquid surface of the dopant-added melt is detected based on a result of the image-capturing, and the crucible is moved upward so that a distance between the liquid surface and a lower end of the heat shield becomes at a predetermined value.
- a laser beam is emitted onto a liquid surface of the dopant-added melt exposed through the cut and a reflected light of the laser beam is received, a height of the liquid surface of the dopant-added melt is detected based on a result of the received reflected light, and the crucible is moved upward so that a distance between the liquid surface and a lower end of the heat shield becomes at a predetermined value.
- the height of the liquid surface of the dopant-added melt can be accurately detected using the image-capturing unit and the laser beam, so that the quality of the monocrystalline silicon can be further stabilized.
- the heat shield includes a downwardly tapered cylindrical portion in a form of a hollow truncated cone, and an annular portion projecting from a lower end of the cylindrical portion to a center of the cylindrical portion.
- the straight body is configured to produce a 200-mm diameter silicon wafer, and a resistivity at a lower end of the straight body of the grown monocrystalline silicon is in a range from 0.5 m ⁇ cm to 0.7 m ⁇ cm.
- the straight body is configured to produce a 300-mm diameter silicon wafer, and a resistivity at a lower end of the straight body of the grown monocrystalline silicon is in a range from 0.78 m ⁇ cm to 1.0 m ⁇ cm.
- a heat shield according to another aspect of the invention is configured to be installed in a monocrystal pull-up apparatus comprising: a crucible configured to receive a dopant-added melt including a silicon melt and red phosphorus added to the silicon melt; a crucible driver configured to vertically move and rotate the crucible; a pull-up portion configured to pull up a seed crystal after bringing the seed crystal into contact with a dopant-added melt to grow the monocrystalline silicon; and a chamber configured to house the crucible and the heat shield, the heat shield being disposed above the crucible to surround the monocrystalline silicon, the heat shield including: a cylindrical portion comprising a circular hollow cylindrical lower end portion; and an annular portion projecting from the lower end portion of the cylindrical portion toward a center of the cylindrical portion, where the annular portion is provided with at least one cut recessed from an inner periphery of the annular portion to an outer periphery thereof, the annular portion being configured to satisfy formulae (6), (7) below, ( C+ 30
- C represents a radius (mm) of a straight body of the monocrystalline silicon
- R represents an inner radius (mm) of the annular portion.
- An annular meniscus is formed around a growing monocrystalline silicon due to surface tension at and near a growth surface of the monocrystalline silicon.
- a distance between an outer circumference of the monocrystalline silicon to an outer periphery of the meniscus (referred to as “meniscus width” hereinafter) is determined by physical properties of the dopant-added melt, and thus is substantially constant irrespective of the size of the monocrystalline silicon.
- the shape of the meniscus becomes flatter toward the outer periphery.
- the shape of the cut can be appropriately imaged at a position outside a predetermined position on the surface of the meniscus, and the reflecting direction can be easily predicted, allowing the light receiver to be easily located at an appropriate position.
- the predetermined position is a position 30 mm away from the inner periphery of the meniscus.
- a region of the liquid surface affecting detection of the height of the liquid surface, which is located between the inner periphery of the meniscus and the position remote from the inner periphery by 30 mm, will be referred to as a detection-affecting region hereinafter.
- a region of the liquid surface outside the detection-affecting region, which does not affect the detection of the height of the liquid surface will be referred to as a detection-non-affecting region hereinafter.
- the numeral “30” in the formula (6) represents a width of the detection-affecting region.
- the position of the deepest portion of the cut in a top plan can be located outside the detection-affecting region, so that the detection-non-affecting region can be exposed through the cut.
- the height of the liquid surface of the dopant-added melt can be accurately detected by capturing the image of the exposed detection-non-affecting region or emitting laser beam onto the detection-non-affecting region.
- the quality of the monocrystalline silicon can thus be stabilized by producing the monocrystalline silicon based on the detection results.
- the temperature distribution in the dopant-added-melt liquid surface in the outer circumferential direction of the monocrystalline silicon can be stabilized, so that the occurrence of dislocation at the top portion of the monocrystalline silicon can be restrained.
- the cut is configured to satisfy a formula (8) below, D ⁇ R ⁇ 0.08 (8)
- D represents a maximum depth (mm) of the cut in a top plan of the annular portion.
- the maximum depth of the cut in a top plan is a value subtracting R used in the formula (6) from A used in the formula (2) (A herein represents a distance from the center of the annular portion to a radially deepest portion of the annular portion in the cut).
- the maximum depth represents a distance from the radially deepest portion of the annular portion in the cut to the inner periphery of the annular portion assuming that the cut is not present.
- the cut is configured to satisfy formulae (9) and (10) below, 0.051 ⁇ H/L (9) H/L ⁇ 0.070 (10)
- H represents a maximum width (mm) of the cut in a top plan of the annular portion
- L represents a length (mm) of an inner circumference of the annular portion assuming that the cut is not present.
- the at least one cut is a single cut.
- a monocrystal pull-up apparatus includes: a crucible configured to receive a dopant-added melt comprising a silicon melt and red phosphorus added to the silicon melt; a crucible driver configured to vertically move and rotate the crucible; a pull-up portion configured to pull up a seed crystal after bringing the seed crystal into contact with the dopant-added melt to grow the monocrystalline silicon; the heat shield according to the above aspect of the invention, the heat shield being disposed above the crucible to surround the monocrystalline silicon; and a chamber configured to house the crucible and the heat shield.
- FIG. 1 schematically illustrates a remelt growth area.
- FIG. 2 schematically illustrates a configuration of a monocrystal pull-up apparatus according to first and third exemplary embodiments of the invention.
- FIG. 3 schematically illustrates a configuration of a heat shield according to the first exemplary embodiment.
- FIG. 4 is a graph showing an exemplary resistivity distribution in a monocrystalline silicon according to the first exemplary embodiment.
- FIG. 5 schematically illustrates a configuration of a monocrystal pull-up apparatus according to a second exemplary embodiment of the invention.
- FIG. 6 is a cross-sectional view showing a configuration of a heat shield according to a modification of the invention.
- FIG. 7A is a cross-sectional view showing a configuration of a heat shield according to another modification of the invention.
- FIG. 7B is a cross-sectional view showing a configuration of a heat shield according to still another modification of the invention.
- FIG. 8 is a cross-sectional view showing a configuration of a heat shield according to further modification of the invention.
- FIG. 9 is a cross-sectional view showing a configuration of a heat shield according to still further modification of the invention.
- a monocrystal pull-up apparatus 1 which is usable for CZ (Czochralski) method, includes a pull-up apparatus body 2 , a liquid surface detector 3 , and a controller 4 .
- the pull-up apparatus body 2 includes a chamber 21 , a crucible 22 , a crucible driver 23 , a heater 24 , a heat insulating cylinder 25 , a pull-up portion 26 , and a heat shield 27 .
- a gas inlet 211 for introducing inert gas (e.g. Ar gas) into the chamber 21 is provided at an upper part of the chamber 21 .
- a gas outlet 212 through which the gas in the chamber 21 is discharged when a vacuum pump (not shown) is driven, is provided at a lower part of the chamber 21 .
- polycrystalline silicon i.e. material of the silicon wafer
- the crucible driver 23 vertically moves the crucible 22 at a predetermined speed and simultaneously rotates the crucible 22 at a predetermined speed around a support shaft 231 connected to a lower end of the crucible 22 .
- the heater 24 is disposed outside the crucible 22 to heat the crucible 22 .
- the heat insulating cylinder 25 is disposed to surround the crucible 22 and the heater 24 .
- the pull-up portion 26 includes a pull-up drive portion 261 and a pull-up cable 262 whose first end is connected to the pull-up drive portion 261 .
- the pull-up drive portion 261 vertically moves and rotates the pull-up cable 262 at a predetermined speed.
- a seed holder 263 for holding a seed crystal or a doping device (not shown) is attached to a second end of the pull-up cable 262 .
- the doping device is a device for doping the silicon melt M in the crucible 22 with red phosphorus (dopant) to provide a dopant-added melt MD.
- the heat shield 27 has a circular hollow cylindrical lower end portion and surrounds a monocrystalline silicon SM at a part above the crucible 22 .
- the heat shield 27 includes a downwardly tapered cylindrical portion 271 in a form of a hollow truncated cone, and an annular portion 272 in a form of an annular plate projecting from a lower end of the cylindrical portion 271 toward the center of the cylindrical portion 271 .
- a single cut 273 recessed toward an outer periphery is provided to an inner periphery of the annular portion 272 on a near side in FIG. 2 (i.e. in +Y direction).
- the heat shield 27 is preferably configured to satisfy formulae (6) and (7) below. ( C+ 30) ⁇ 0.926 ⁇ R (6) R ⁇ 1.27 ⁇ C (7)
- the detection-affecting region MD 21 is an annular (in a top plan) and curved (in a vertical cross section) region contained in a meniscus MD 2 .
- the detection-affecting region MD 21 affects detection of a height of a liquid surface by the liquid surface detector 3 .
- a detection-non-affecting region MD 22 located outside the detection-affecting region MD 21 which is a flat or substantially flat region in a vertical cross section, does not affect the height detection of the liquid surface.
- the cut 273 is preferably configured to satisfy formulae (8), (9) and (10) below. D ⁇ R ⁇ 0.08 (8)
- L a length (mm) of an inner circumference of the annular portion 272 assuming that the cut 273 is not present
- the cut 273 is preferably configured to satisfy a formula (11) below in addition to the formula (8).
- the shape of the cut 273 satisfying the formula (6) as described above allows the deepest portion 274 of the cut 273 to be located outside the detection-affecting region MD 21 in a top plan.
- the cut 273 is configured to be wide enough to satisfy the formula (9) and deep enough to satisfy the formula (11). As a result, the detection-non-affecting region MD 22 can be sufficiently exposed through the cut 273 in a top plan.
- R in the formulae (7), (11) can also be defined as “an inner radius of the lower end portion of the heat shield 27 ” and L in the formulae (9), (10) can also be defined as “a length of an inner circumference of the lower end portion of the heat shield 27 assuming that the cut 273 is not present.”
- the liquid surface detector 3 is configured to detect a height of the liquid surface MD 1 of the dopant-added melt MD.
- the liquid surface detector 3 includes an image capturing unit 31 and a position calculator 32 .
- the image capturing unit 31 includes, for instance, a CCD camera, which captures an image of the liquid surface MD 1 of the dopant-added melt MD exposed through the cut 273 .
- the position calculator 32 is configured to calculate the height of the liquid surface MD 1 based on the result of the image-capturing of the image capturing unit 31 .
- the controller 4 is configured to control, for instance, a gas flow rate and furnace pressure in the chamber 21 , a temperature for heating the crucible 22 by the heater 24 , and rotation speeds of the crucible 22 and the monocrystalline silicon SM, based on information stored in a memory 41 or input from an operator, the result of the height detection of the liquid surface MD 1 by the liquid surface detector 3 , and the like, to produce the monocrystalline silicon SM.
- a monocrystalline silicon SM capable of providing a 200-mm diameter silicon wafer from the straight body SM 3 will be described in this exemplary embodiment.
- a monocrystalline silicon SM capable of providing a silicon wafer having a different diameter e.g. 300 mm and 450 mm may alternatively be produced.
- the diameter of the straight body SM 3 is preferably in a range from 201 mm to 230 mm when the diameter of the silicon wafer is 200 mm, in a range from 301 mm to 340 mm when the diameter of the silicon wafer is 300 mm, and in a range from 451 mm to 510 mm when the diameter of the silicon wafer is 450 mm.
- resistivity at the lower end of the straight body SM 3 is preferably in a range from 0.5 m ⁇ cm to 0.7 m ⁇ cm as shown in, for instance, Examples 1 and 2 in FIG. 4 .
- resistivity at the lower end of the straight body SM 3 is preferably in a range from 0.78 m ⁇ cm to 1.0 m ⁇ cm, as shown in, for instance, Examples 3 and 4 in FIG. 4 .
- the controller 4 of the monocrystal pull-up apparatus 1 sets pull-up conditions for satisfying the required quality (e.g. resistivity and oxygen concentration) of the monocrystalline silicon SM.
- the pull-up conditions include, for instance, flow rate of the inert gas, pressure inside the chamber 21 , rotation speeds of the crucible 22 and the monocrystalline silicon SM, and heating conditions of the heater 24 . It should be noted that the conditions may be inputted by the operator, or may be calculated by the controller 4 based on the target oxygen concentration and the like inputted by the operator.
- the controller 4 controls the heater 24 to heat the crucible 22 , thereby melting polysilicon material (silicon material) and a dopant in a form of red phosphorus in the crucible 22 to produce the dopant-added melt MD.
- the controller 4 then starts introduction of a predetermined flow rate of inert gas through the gas inlet 211 into the chamber 21 , and reduces the pressure inside the chamber 21 to create and maintain a depressurized inert atmosphere in the chamber 21 .
- the controller 4 immerses the seed crystal in the dopant-added melt MD and pulls up the pull-up cable 262 while rotating the crucible 22 and the pull-up cable 262 in a predetermined direction, thereby growing the monocrystalline silicon SM including a neck SM 1 , a shoulder SM 2 , the straight body SM 3 , and a tail (not shown).
- the monocrystal pull-up apparatus 1 While the monocrystalline silicon SM is growing, the monocrystal pull-up apparatus 1 upwardly moves the crucible 22 so that a distance K between the liquid surface MD 1 and a lower face of the annular portion 272 becomes at a predetermined value.
- This process for controlling the upward movement of the crucible 22 so that the distance K stays at the predetermined value will be referred to as a “gap control” hereinafter.
- the distance K is preferably changed depending on the solidification rate of the monocrystalline silicon SM in order to obtain a monocrystalline silicon with stable quality.
- the image capturing unit 31 of the liquid surface detector 3 captures an image of the liquid surface MD 1 of the dopant-added melt MD exposed through the cut 273 .
- the image capturing unit 31 can easily capture a non-distorted mirror image of the cut 273 reflected on the detection-non-affecting region MD 22 .
- the position calculator 32 calculates the height of the liquid surface MD 1 based on the position of the mirror image of the cut 273 captured by the image capturing unit 31 .
- the controller 4 performs the gap control based on the result of the calculation by the position calculator 32 .
- the heat shield 27 satisfying the formula (7) is used in the first exemplary embodiment, heat dissipation from the dopant-added melt MD through the gap between the monocrystalline silicon SM and the annular portion 272 can be reduced.
- the temperature gradient at the bottom portion of the monocrystalline silicon SM in the pulling direction can thus be increased. Accordingly, the occurrence of dislocation at the bottom portion due to compositional supercooling can be restrained.
- the cut 273 provided to the heat shield 27 ensures a sufficient liquid-surface exposure area for checking the position of the liquid surface MD 1 in a top plan.
- the gap control can thus be conducted while the monocrystalline silicon SM is grown. Accordingly, thermal hysteresis and impurity concentration in each of batches of the monocrystalline silicon SM can be made constant, so that the quality of the monocrystalline silicon SM can be stabilized.
- the cut 273 is configured to satisfy the formulae (8), (10), the temperature distribution in the liquid surface MD 1 in the outer circumferential direction of the monocrystalline silicon SM can be stabilized as compared with an instance in which the formula (8) is not satisfied (i.e. the cut 273 is too deep) and an instance in which the formula (10) is not satisfied (i.e. the cut 273 is too wide). Accordingly, the occurrence of dislocation at the top portion of the monocrystalline silicon SM due to remelting can be restrained.
- the maximum width of the cut 273 can be increased to secure a sufficient liquid-surface exposure area. Consequently, the height of the liquid surface MD 1 can be easily checked.
- a monocrystal pull-up apparatus 1 A according to the second exemplary embodiment differs from the monocrystal pull-up apparatus 1 according to the first exemplary embodiment in that a liquid surface detector 3 A using laser beam is provided instead of the liquid surface detector 3 for detecting the height of the liquid surface MD 1 .
- the liquid surface detector 3 A includes a light emitter 31 A, a light receiver 32 A, and a position calculator 33 A.
- the light emitter 31 A of the liquid surface detector 3 A emits laser beam NL to the liquid surface MD 1 of the dopant-added melt MD exposed through the cut 273 .
- the light receiver 32 A receives reflected light NR from the liquid surface MD 1 .
- the laser beam NL enters the detection-non-affecting region MD 22 and a reflection angle of the reflected light NR becomes substantially equal to an incident angle of the laser beam NL. Accordingly, a reflecting direction of the reflected light NR can be easily calculated, so that the light receiver 32 A can be easily placed at an appropriate position.
- the position calculator 33 A calculates the height of the liquid surface MD 1 based on a light-receiving position of the reflected light NR by the light receiver 32 A.
- the controller 4 then performs the gap control based on the result of the calculation by the position calculator 33 A.
- a monocrystal pull-up apparatus 1 B according to the third exemplary embodiment differs from the monocrystal pull-up apparatus 1 according to the first exemplary embodiment in that a heat shield 27 B including an annular portion 272 B without any cut is used instead of the heat shield 27 including the annular portion 272 provided with the cut 273 .
- the image capturing unit 31 of the liquid surface detector 3 captures an image of the liquid surface MD 1 exposed through a gap between the monocrystalline silicon SM and an inner periphery of the annular portion 272 B, and the position calculator 32 calculates the height of the liquid surface MD 1 .
- the controller 4 then performs the gap control based on the result of the calculation by the position calculator 32 .
- the heat shield 27 B is preferably configured to satisfy a formula (12) below in addition to the above formula (7). 1.17 ⁇ C ⁇ R (12)
- the annular portion 272 B is kept from touching the monocrystalline silicon SM.
- the heat shield 27 B satisfying the formula (7) can reduce heat dissipation from dopant-added melt MD through the gap between the monocrystalline silicon SM and the annular portion 272 B. Accordingly, the temperature gradient of the bottom portion of the monocrystalline silicon SM in the pulling direction can be increased, so that occurrence of dislocation at the bottom portion due to compositional supercooling can be restrained.
- the heat shield 27 for the monocrystal pull-up apparatus 1 and the monocrystal pull-up apparatus 1 A may be replaced with a heat shield 27 C or a heat shield 27 D shown in FIGS. 7A and 7B , respectively.
- a cut 273 C and a cut 275 C are provided to an annular portion 272 C of the heat shield 27 C.
- the cut 273 C and the cut 275 C are symmetrical across the center of the monocrystalline silicon SM.
- a cut 273 D and a cut 275 D are provided to an annular portion 272 D of the heat shield 27 D.
- the heat shields 27 C, 27 D preferably satisfy the formulae (6) and (7).
- the cuts 273 C, 275 C, 273 D and 275 D preferably satisfy the formulae (8), (9), (10) and (11).
- Maximum widths H 1 of the cuts 273 C and 273 D and maximum widths H 2 of the cuts 275 C and 275 D each may satisfy the formulae (9) and (10).
- a total width H of the maximum width H 1 and the maximum width H 2 may satisfy the formulae (9) and (10).
- “D” in the formulae (8) and (11) represents a depth of each of deepest portions 274 C, 276 C, 274 D and 276 D of the respective cuts 273 C, 275 C, 273 D and 275 D.
- the heat shields 27 for the monocrystal pull-up apparatus 1 and the monocrystal pull-up apparatus 1 A may be replaced with a heat shield 27 E or a heat shield 27 F having a circular hollow cylindrical lower end portion, as shown in FIGS. 8 and 9 , respectively.
- the heat shield 27 E consists of a cylindrical portion 271 E in a form of a hollow truncated cone that is tapered downward.
- An upwardly extending cut 273 E is provided at a part of an outer circumference of the cylindrical portion 271 E of the heat shield 27 E.
- an outward projection 277 E in a form of a flange extending outward from a lower end of the cylindrical portion 271 E may be provided as shown in chain double-dashed lines.
- the heat shield 27 E preferably satisfies a formula (1) below and the above formula (6).
- the cut 273 E preferably satisfies formulae (4) and (5) below and the above formulae (8) and (11). It should be noted that “D” in the formulae (8) and (11) represents a depth of a deepest portion 274 E of the cut 273 E in a top plan. R ⁇ 1.27 ⁇ C (1)
- the heat shield 27 F consists of a cylindrical portion 271 F in a form of a hollow truncated cone that is tapered downward and has no cut.
- the heat shield 27 F preferably satisfies the above formula (12) in addition to the formula (1).
- the heat shield 27 B as shown in FIG. 6 may be used in the monocrystal pull-up apparatus 1 A shown in FIG. 5 .
- the number of cuts provided to the annular portion of the heat shield is three or more in some embodiments.
- the shape of the cut(s) is different from the shape of the above-described cut(s) in some embodiments (e.g. semi-circular).
- the height of the liquid surface MD 1 is visually checked in some embodiments.
- the crucible 22 is moved upward with reference to past production results without detecting the height of the liquid surface MD 1 in some embodiments.
- the shape of the cylindrical portions 271 , 271 E and 271 F may be designed in any manner as long as the cylindrical portions each have a circular hollow cylindrical lower end portion.
- the cylindrical portions may be a downwardly flared hollow truncated cone, a cylinder of constant diameter at any vertical position thereof, a combination of a hollow truncated cone and a cylinder, and a combination of a tapered hollow truncated cone and a flared hollow truncated cone.
- a heat shield with no cut in the annular portion as shown in FIG. 6 was prepared. Inner radius R of the annular portion was 140 mm as shown in Table 1 below.
- the heat shield of the Experimental Example 1 was set in a monocrystal pull-up apparatus as shown in FIG. 2 .
- a monocrystalline silicon for a 200-mm wafer was produced with the monocrystal pull-up apparatus.
- a straight body of the monocrystalline silicon had a radius C of 102.5 mm and target resistivity at the lower end of the straight body was in a range from 0.5 m ⁇ cm to 0.7 m ⁇ cm as shown in Example 1 or 2 in FIG. 4 .
- the dopant was red phosphorus.
- a monocrystalline silicon was produced under the same conditions as those in Experimental Example 1 except that the inner radius R of the heat shield was set at a value shown in Table 1, the monocrystalline silicon was for a 300-mm wafer with a straight body having a radius C of 153.5 mm, and target resistivity at the lower end of the straight body was in a range from 0.78 m ⁇ cm to 1.0 m ⁇ cm as shown in Example 3 or 4 in FIG. 4 .
- Table 1 shows the ratio of the inner radius of annular portion (R/C), the number of produced monocrystalline silicon (the number of trials), the number of monocrystalline silicon with no dislocation at the bottom portion (the number of acceptable samples) and the dislocation-free rate at the bottom portion (the number of acceptable samples/the number of trials) in Experimental Examples 1 to 9.
- a prepared heat shield had a single cut in the annular portion as shown in FIG. 3 .
- An inner radius R of the annular portion, a maximum width H of the cut in a top plan, and a distance A from the center of the annular portion to the deepest portion of the cut were set as shown in Table 2 below.
- the heat shield of the Experimental Example 10 was set in a monocrystal pull-up apparatus as shown in FIG. 2 .
- a monocrystalline silicon for a 200-mm wafer was produced with the monocrystal pull-up apparatus.
- Target resistivity at the lower end of the straight body was 0.7 m ⁇ cm or less as shown in Example 1 or 2 in FIG. 4 .
- a monocrystalline silicon was produced under the same conditions as those in Experimental Example 10 except that the inner radius R, the maximum width H, and the distance A of the heat shield were set as shown in Table 2.
- the cut width ratio (H/L) in each of Experimental Examples 11 to 13 was in a range from 0.065 to 0.070, and the cut width ratio (R/A) was in a range from 0.926 to 0.969.
- the gap control was stably conducted when the distance K between the liquid surface MD 1 and the lower face of the annular portion 272 could be controlled within a range of a preset value ⁇ 2 mm.
- the dislocation-free rate at the top portion is lowered when H/L exceeds 0.070 (i.e. when the cut width is too large) because the temperature distribution at the dopant-added-melt liquid surface in the outer circumferential direction of the monocrystalline silicon becomes unstable and, consequently, a remelt growth area caused by remelting is generated at the shoulder of the monocrystalline silicon, causing dislocation at the top portion.
- the heat shield configured to satisfy the formulae (9) and (10) can restrain the occurrence of dislocation at the top portion and allows an optimal gap control to produce a monocrystalline silicon with stable quality.
- the dislocation-free rate at the top portion is lowered when R/A is less than 0.926 (i.e. when the cut is too deep) because, as in an instance where the cut width is too wide, the temperature distribution at the dopant-added-melt liquid surface in the outer circumferential direction of the monocrystalline silicon becomes unstable.
- the detection-non-affecting region of the meniscus is preferably exposed through the cut in order to conduct more stable gap control and enhance the quality of the monocrystalline silicon. It is thus necessary to locate the deepest portion of the cut at an outside of the detection-affecting region.
- the width of the detection-affecting region is 30 mm and the minimum value of R/A (cut depth ratio) is determined to be 0.926 according to the formula (2).
- the formula (6) can be derived by assigning “C (radius of monocrystalline silicon)+30 (width of detection-affecting region)” to “A” in the formula (2).
- a formula “122.7 ⁇ R” can be derived by assigning the value C in each of Experimental Examples 10 to 13 into the formula (6).
- the Experimental Examples 11 to 13 satisfy the above formula, while the Experimental Example 10 does not satisfy the above formula.
- the heat shield configured to satisfy the formula (6) can stabilize the gap control and, consequently, can produce a monocrystalline silicon with more stable quality.
- the maximum depth D of the cut is represented by “A ⁇ R.” Since the minimum value of R/A is determined to be 0.926 according to the formula (2), the formula (8) can be derived by assigning “A ⁇ R” into the formula (2) and modifying the formula.
- the heat shield configured to satisfy the formula (8) in addition to the formula (6) can stabilize the gap control and, consequently, produce a monocrystalline silicon with more stable quality.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
R≤1.27×C (1)
0.926≤R/A (2)
R/A≤0.969 (3)
0.051≤H/L (4)
H/L≤0.070 (5)
(C+30)×0.926≤R (6)
R≤1.27×C (7)
D≤R×0.08 (8)
0.051≤H/L (9)
H/L≤0.070 (10)
(C+30)×0.926≤R (6)
R≤1.27×C (7)
D≤R×0.08 (8)
0.051≤H/L (9)
H/L≤0.070 (10)
R×0.03≤D (11)
1.17×C≤R (12)
R≤1.27×C (1)
0.051≤H/L (4)
H/L≤0.070 (5)
| TABLE 1 | ||||||||
| Inner Radius of | ||||||||
| Annular Portion | Ratio of | |||||||
| (Lower End | Inner Radius | Number of | Dislocation- | |||||
| Target | Portion of Heat | Monocrystal | of Annular | Number of | Acceptable | Free Rate at | ||
| Resistivity | Shield) R(mm) | Radius C(mm) | Portion R/C | Trials | Samples | Bottom Portion | ||
| Ex. 1 | 0.7 mΩ · cm or | 140 | 102.5 | 1.37 | 2 | 0 | 0% |
| Ex. 2 | less | 135 | 102.5 | 1.32 | 3 | 1 | 33% |
| Ex. 3 | 130 | 102.5 | 1.27 | 5 | 4 | 80% | |
| Ex. 4 | 125 | 102.5 | 1.22 | 2 | 2 | 100% | |
| Ex. 5 | 120 | 102.5 | 1.17 | 1 | 1 | 100% | |
| Ex. 6 | 1.0 mΩ · cm or | 200 | 153.5 | 1.30 | 2 | 0 | 0% |
| Ex. 7 | less | 195 | 153.5 | 1.27 | 3 | 2 | 67% |
| Ex. 8 | 190 | 153.5 | 1.24 | 4 | 4 | 100% | |
| Ex. 9 | 185 | 153.5 | 1.21 | 8 | 8 | 100% | |
Analysis
| TABLE 2 | |||||
| Ex. 10 | Ex. 11 | Ex. 12 | Ex. 13 | ||
| Inner Radius R of Annular Portion | 117.5 | 125.0 | 125.0 | 125.0 |
| (Lower End of Heat Shield) (mm) | ||||
| Radius C of Monocrystalline | 102.5 | 102.5 | 102.5 | 102.5 |
| Silicon (mm) | ||||
| Ratio of Inner Radius of Annular | 1.15 | 1.22 | 1.22 | 1.22 |
| Portion R/C | ||||
| Cut Maximum Width H (mm) | 56 | 51 | 55 | 55 |
| Length L (mm) (=2πR) of Inner | 738 | 785 | 785 | 785 |
| Circumference of Annular Portion | ||||
| (Lower End Portion of Heat | ||||
| Shield) Assuming That Cut Is Not | ||||
| Present | ||||
| Ratio of Cut Width H/L | 0.076 | 0.065 | 0.070 | 0.070 |
| Distance A (mm) from Center of | 129 | 132 | 135 | 129 |
| Annular Portion (Lower End of | ||||
| Heat Shield) to Deepest Portion of | ||||
| Cut | ||||
| Cut Depth Ratio R/A | 0.911 | 0.947 | 0.926 | 0.969 |
| Cut Maximum Depth D (mm) | 11.5 | 7.0 | 10.0 | 4.0 |
| (=A − R) | ||||
| Number of Trials | 5 | 20 | 5 | 10 |
| Number of Acceptable Samples | 1 | 17 | 4 | 9 |
| Dislocation-Free Rate at Top | 20% | 85% | 80% | 90% |
| Portion | ||||
| Gap Control Stability | B | A | A | A |
| A: Stable, B: Unstable | ||||
| Whether Formula (6) (122.7 ≤ R) | B | A | A | A |
| Is Satisfied | ||||
| A: Satisfied, B: Not Satisfied | ||||
| Value of R × 0.08 | 9.4 | 10 | 10 | 10 |
| Whether Formula (8) (D ≤ R × | B | A | A | A |
| 0.08) Is Satisfied | ||||
| A: Satisfied, B: Not Satisfied | ||||
Analysis
0.926≤R/A (2)
R/A≤0.969 (3)
Claims (18)
R≤1.27×C (1)
0.926≤R/A (2)
R/A≤0.969 (3)
R≤1.27×C (1)
0.051≤H/L (4)
H/L≤0.070 (5)
(C+30)×0.926≤R (6)
R≤1.27×C (7)
D≤R×0.08 (8)
0.051≤H/L (9)
H/L≤0.070 (10)
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| JPJP2016-249119 | 2016-12-22 | ||
| JP2016-249119 | 2016-12-22 | ||
| JP2016249119A JP6631496B2 (en) | 2016-12-22 | 2016-12-22 | Method for producing silicon single crystal, heat shield, and single crystal pulling apparatus |
| PCT/JP2017/036992 WO2018116590A1 (en) | 2016-12-22 | 2017-10-12 | Method for producing silicon single crystal, heat shield, and single crystal pulling device |
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| US20200115821A1 US20200115821A1 (en) | 2020-04-16 |
| US11047065B2 true US11047065B2 (en) | 2021-06-29 |
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| US (1) | US11047065B2 (en) |
| JP (1) | JP6631496B2 (en) |
| KR (1) | KR102253558B1 (en) |
| CN (1) | CN110268105B (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US12297560B2 (en) | 2019-12-24 | 2025-05-13 | Sumco Corporation | Method for manufacturing monocrystalline silicon by the Czochralski process by pulling a first straight body having a first diameter and a second straight body having a second diameter larger than the first diameter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7080017B2 (en) * | 2017-04-25 | 2022-06-03 | 株式会社Sumco | n-type silicon single crystal ingots, silicon wafers, and epitaxial silicon wafers |
| DE112018003320T5 (en) | 2017-06-29 | 2020-03-19 | Sumco Corporation | Process for the production of silicon single crystal |
| JP2023170512A (en) * | 2022-05-19 | 2023-12-01 | 株式会社Sumco | Single crystal pulling equipment |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018116590A1 (en) | 2018-06-28 |
| DE112017006524T5 (en) | 2019-12-05 |
| JP6631496B2 (en) | 2020-01-15 |
| KR20190089976A (en) | 2019-07-31 |
| CN110268105B (en) | 2021-06-08 |
| US20200115821A1 (en) | 2020-04-16 |
| DE112017006524B4 (en) | 2024-07-18 |
| KR102253558B1 (en) | 2021-05-18 |
| CN110268105A (en) | 2019-09-20 |
| JP2018104206A (en) | 2018-07-05 |
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